Acid wool dyestuffs and process of preparing them



Patented Mar. 10, 1931 UNITED STATES PATENT OFFICE WILHELM ECKERT, F FRANKFORT-ON-THE-MAIN-HOCHST, GERMANY, ASSIGNOR TO GENERAL ANILINE WORKS, INC., 01 NEW YORK, N. Y., A CORPORATION OF DELA- WARE ACID WOOL DYESTUFFS AND PROCESS OF PREPARING THEM No Drawing. Application filed October 20, 1928, Serial No. 313,954, and in Germany October 29, 1927.

My present invention relates to new dye- V stuffs and to a process of preparing them.

I have found that new dyestuffs ielding extremely clear shades are obtained y caus- 5 ing a compound of the general formula:

wherein X represents the sulfonic or the sulfaminic acid group and Y represents a monovalent substituent or hydrogen and an- 1 other compound of the group consisting of NH: N Ha, a1kyl-NH2, 8I&lkylNHg, aryl-NHz, and ary1 (oz-tho), NH:

(the aryl residues being substituted or not) to act upon each other 11113118 presence of water at a temperature of about 100 C. The A reaction may be effected either by a simple heating operation or by heating in an autoclave under pressure. p

The same or similar dyestufis are obtained by transforming the reaction products of naphthalic anhydride, or a derivative thereof, with ammonia, an aliphatic or aromatic I amine into the sulfonic acids or sulfamic acids respectively, or by subjecting naphthalic anhydride or a derivative thereof to reaction with a sulfonic acid of an amine.

The new dyestufis, to which the following formula may be attributed wherein X represents the sulfonic or the sulfaminlc acld group, Y represents a monovamy invention, but they are not intended to limit it thereto, the parts being by weight.

1. parts of 4-sodium-sulfamin-1.8-naphthalenedicarboxylic anhydride of the following formula:

are heated to boiling in 800 parts of water with 30 parts of ortho-phenyldiamine. When the reaction is finished, the undissolved part of the product is filtered off by suction and the dyestuif is salted out in the usual manner; it has probably the following formula and forms an orange colored powder, dyeing woolfrom an acid hath orange yellow tints.

2. When, instead of ortho-phenylenediis obtained, dyein'g'woolfrom an acid bath a amine the corresponding quantity of aniline is used, a dyestuif of the following formula:

bright clear yellow tint, which is superior as regardsitsigreenish huetothesknown qui'noline yellow colors. Artificial silk made. of cellulose esters or cellulose ethers is dyed clear greenish yell'ow tints of a. great intensity fanfd a'b-rightgreenish fluorescence. 1

3. parts of 4=sodium sulfamin-lfi nap-hthalenedicarboxylic anhydrideand 200 parts of ammonia are heated in an autoclave to 100 C. After having workedup theprodis ramm eaving the am ng formula nseam which dyes wool and acetate silk -from an acid bath a very clear yellow tint.

4. 10 parts of the-sulfonicacid-of t-amino- 1'.8-naphthalenedicarboxylic anhydride, obtained by sulfonation of 'i-azmino-lfina ohthalio anhydride, are heated to boiling with V 10 partsof ortho-pheny-len'ediamine and 200 parts of water. WVhen the reaction is complete, "the mass isfiltered by suction and the resulting. dyestulf is salted out; it has probably :thefoll owing -formula:

and dyes wool an orange tint. The prodv not obtained by the reaction of the acid mentioned in Exam ple"4,*with ammonia shows aclariyellow color.v

5. 10 parts of 4-amino-l;8-naphthalimide, obtainedby treatmentg 0f aminonap'hthalic a-nhydride with ammonia, are heated with 100 parts of sulfuric acid monohydra-te to a te1nperature of about 110 C.,- till a test sample taken from the mass has become water-soluble. As soon as this is the case, the mass is poured into water and the dyest'ufi is salted out in the usual manner. 1 It has the following formula:

I {NH oe o0 i V .f I THz altered t-aminonaphthalimide is separated.

The filtrate is then neutralized and salted out.

The sulfamic acid thus obtained has the formula:

V NH, SOaNa and {dyes wool from a bath acidified with acetic'acid clear yellow tints. The dyestufi is furthermore suited for dyeing cellulose esters and cellulose ethers clear yellow shadesof an intense greenish fluorescence.

7. 14.4 parts of -amin'onap-hthalphenyh imide are introducedinto a mixture of 15 partsof chl-orosulfonic acid and 200 parts of pyridine and the whole is heated for 3 hours to 5'060 C. The mass is thensubjected togethe with 30parts of sodium carbonate to distillation with water vapor. The unaltered portion of staminonaphthalphenylimide is then filtered oil and salted out. The resulting product has thefollowing formula misoma and dyes wool from aLbath-acidified with acetic acid bright yellow tints. Acetate silk treated in a dye bath which contains a quantity of about 2.5% of the dyestuff,'calculated upon the weight of the acetate silk, is dyed a clear greenish-yellow tintof a great intensity and an excellent greenish fluorescence.

By using instead of the 4-aminonaphthalphenylimide as per Example 7, 4c-aminonaphthalethylimide or 3-aminonaphthalmethylimide and proceeding as indicated in Example 7, dyestuffs of similar properties are obtained.

8. 10 parts of -aminonapththalic anhydride are heated to boiling with 10 parts of sodium 4-toluidine-3-sulfonate and 200 parts of water on the reflux condenser until the formation of the dyestuif is finished; it is then filtered by suction and the dye is obtained from the aqueous solution in the usualmanner, for instance by saltlng it out. has the following formula:

SOzNa and dyes the animal fiber from an acid bath a very clear yellow tint.

9. 10 parts of 4-amino-sulfo-L8-naphthalenedicarboxylic anhydride, obtained by sulfonation of 4-amino-L8-naphthalic anhy-V dride with sulfonating agents, are heated to boiling with 10 parts of para-toluidine and 100 parts of water for 3-4 hours. The .excess of para-toluidine is then blown off by means ofwater Vapor. After filtration of the solution, the dyestuif separates therefrom on cooling in the form of golden-yellow lamellae. By

salting out the filtrate, a further quantity of the dyestufl can be obtained. This dyestuff has the following formula:

. N- oc be OiNB and is a yellow crystalline powder, which dissolves'in water with a clear yellowtint, with r a strong greenish fluorescence. It dyes the animal fiber from an acid bath a greenish yellow tint, which is superior as regards its greenishchue to the known quinoline yellow dyes possessing at the same time a clearness which has never before been attained.

I claim:

1. The process which comprises causing a compound of the group consisting of (the aryl residues being substituted or not) to act upon a compound of the general formula o o o wherein X represents the sulfonic or the sulfaminic acid group and Y represents a monovalent substituent or hydrogen in the presence of water at a temperature of about 100 C.

2. The process which comprises causing a compound of the group consisting of NH: NHa, alkyl-NHz, aralkyl-NHz, aryl-NH: and aryl NH (ortho),

(the aryl residues being substituted or not) to act upon a compound of the general formula NH: NHa, phenyl-NE and phenyl NH (ortho),

(the phenyl residues being substituted or not) to act upon a compound of the formula:

in the presence of Water at a temperature of about 100 C.

V I v a wherein X represents the sulfonic or the sul- 4. The process which comprises causing para toluidine to'actupon' a compound of the formula:

in the presence of'water ata temperature of about 100 C. V

5. As new products the water soluble dyestufis of the following general formula:

1TH N 6 faminic" acid group, represents a monovalent substituent or hydrogen, R stands for I hydrogen,,alkyl, aralkyl or aryl, (the aryl residue being substituted or not) in which case R is oxygen, orv R and B jointly represent the group 7 j LgN -kphenyl I (the phenyl nucleus being substituted or not) said dyestuffs giving on animal fiber very even and extremely clear tints.

6. As new products the water soluble dyestuffs of the following general formula:

wherein X 'represents the sulfonicacid group and Y represents the amino group, or X ;v represents the-sulfaminic acid group'and Y stands for hydrogen, R stands for hydrogen, 'alkyl, aralkyl, or aryl, (the aryl residue being substituted or not) in which case R is oxygen, or R; andR jjointly represent the,

, (the phenyl nucleus being substituted or not) said dyestuffs givingon animal fiber very;

even and extremely clear tints;

7. Asnew products, water. soluble dyestuffs of the following general formula:

N3 wherein R stands for hydrogen or phenyl, (the-phenyl residue beingsubstituted or not) in which case R isyoxygen or R 'and R jointly represent the group 1 being 'a-yellow crystalline powder dissolving in water to a'clear yellow solution with a strong greenish fluorescence, dyeing the animal fiber from an acid bath a greenish yellow tint.

9. As new productsthe water soluble dye stuffs of the followinggeneral formulawherein R represents hydrogen, alkyl, aralkyl or aryl, X represents the amino group in which case Y stands for a sulfonic acid group or X represents a sulfaminicacid,

group in which case Y stands for hydrogen, said dyestufis giving on animal ,fibervery even and extremely clear tints. I c 130 10. As new products the water soluble dyestuflts of the following general formula:

I oo bo wherein R represents hydrogen, alkyl, aralkyl or aryl, said dyestuffs giving on animal fiber from an acid bath very evenand extremely clear tints. 4

'11. As new products the water soluble'dyestuffs of the following general formula: I

alryl N 06 to SO|H 7 NH: said dyestufls giving on animal fiber from an acid bath very even and extremely clear tints.

12. As a new product the water soluble dyestuffs of the following general formula:

phenyl said dyestufls givingon animal fiber from an acid bath very even and extremely clear tints.

In testimony whereof, I affix my signature.

WILHELM ECKERT. 

